全光型石英增强光声光谱

设计并演示了一种全光型石英增强光声光谱技术, 该技术在传统的石英增强光声光谱系统中增加了另一束探测光束, 把与气体浓度成正比的石英晶振振臂的振动幅值转化为探测光束的强度变化, 实现了探测气体处无电子元件的全光学系统. 如此的设计使该系统具有较强的抗电磁干扰能力和非常小的传感头体积, 能够用于探测空间受限或探测环境恶劣的情况下, 并实现远距离探测. 在这种配置下, 探测大气压下的水汽, 获得的噪声等效吸收系数为1.13×10^-6 cm^-1W/√Hz. 进一步讨论了优化系统和提升其探测灵敏度的途径. 关键词： 石英增强光声光谱 音叉式石英晶振 气体传感     

Off-beam quartz-enhanced photoacoustic spectroscopy with LEDs

A photoacoustic ozone sensor based on quartz-enhanced photoacoustic spectroscopy is presented. Instead of a laser, a UV-LED at 285 nm is utilized as light source. Using an acoustical resonator in off-beam configuration, it is feasible to align the light of the LED through the resonator tube. The sensor is integrated in a miniaturized flow-through gas cell which allows fast gas exchange. The sensor performance and the influence of the speed of sound on the measurement signal are investigated. For the detection of ozone in the Hartley band, a detection limit of S = 1.27 ± 0.08 ppmv (1σ) and a noise equivalent absorption sensitivity of D = (3.02 × 10^?8 ± 1 × 10^?10) cm^?1W(Hz)^?1/2 have been achieved.     

光纤倏逝波型石英增强光声光谱技术

采用块状光学准直聚焦透镜组的传统石英增强光声光谱(QEPAS)技术存在体积难以缩减,结构稳定性不佳,无法适应空间狭小、振动复杂的特殊环境等缺点.基于此,将光纤倏逝波技术与QEPAS技术相结合,提出了一种新型微纳结构光纤QEPAS痕量气体检测技术.实验中,为了提高QEPAS系统信号幅值,优化了石英音叉与激光束的空间位置、激光波长调制深度,同时对比了两种不同共振频率的石英音叉,最终采用共振频率较低的30.720 kHz石英音叉作为声波探测元件,获得的检测极限为6.25×10~(-4)(体积分数),归一化噪声等效吸收系数为4.18×10~(-7)cm~(-1).W·Hz~(-1/2).     

Theoretical analysis of a quartz-enhanced photoacoustic spectroscopy sensor

Quartz-enhanced photoacoustic spectroscopy (QEPAS) sensors are based on a recent approach to photoacoustic detection which employs a quartz tuning fork as an acoustic transducer. These sensors enable detection of trace gases for air quality monitoring, industrial process control, and medical diagnostics. To detect a trace gas, modulated laser radiation is directed between the tines of a tuning fork. The optical energy absorbed by the gas results in a periodic thermal expansion which gives rise to a weak acoustic pressure wave. This pressure wave excites a resonant vibration of the tuning fork thereby generating an electrical signal via the piezoelectric effect. This paper describes a theoretical model of a QEPAS sensor. By deriving analytical solutions for the partial differential equations in the model, we obtain a formula for the piezoelectric current in terms of the optical, mechanical, and electrical parameters of the system. We use the model to calculate the optimal position of the laser beam with respect to the tuning fork and the phase of the piezoelectric current. We also show that a QEPAS transducer with a particular 32.8 kHz tuning fork is 2–3 times as sensitive as one with a 4.25 kHz tuning fork. These simulation results closely match experimental data.     

Theoretical analysis of off beam quartz-enhanced photoacoustic spectroscopy sensor

Off beam quartz-enhanced photoacoustic spectroscopy (OB-QEPAS) sensors are based on a recently developed approach to off-beam photoacoustic (PA) detection which employs a quartz tuning fork (QTF) as an acoustic transducer. A microresonator (mR) with a side slit in the middle is used to enhance PA signal. This paper describes a theoretical model of an OB-QEPAS-based sensor. By deriving the acoustic impedances of the mR at two ends and the side slit in the middle in the model, we obtain a formula for numerically calculating the optimal mRs' parameters of OB-QEPAS-based sensor. We use the model to calculate the optimal mRs' lengths with respect to the resonant frequency of the QTF, acoustic velocities inside mRs, inner diameters of mRs, and acoustic conductivities of the mRs' side slits, and found out that the calculated results closely match experimental data. We also investigated the relationship between the mR selected in “on beam” QEPAS, OB-QEPAS, and an acoustic resonator (AR) excited in its first longitudinal mode used in conventional photoacoustic spectroscopy (PAS).     

Formaldehyde sensor using interband cascade laser based quartz-enhanced photoacoustic spectroscopy

A novel continuous-wave mid-infrared distributed feedback interband cascade laser was utilized to detect and quantify formaldehyde (H₂CO) using quartz-enhanced photoacoustic spectroscopy. The laser was operated at liquid-nitrogen temperatures and provided single-mode output powers of up to 12 mW at 3.53 m (2832.5 cm^-1). The noise equivalent (1) detection sensitivity of the sensor was measured to be 2.2×10^-8 cm^-1W(Hz)^-1/2 for H₂CO in ambient air, which corresponds to a detection limit of 0.6 parts in 10⁶ by volume (ppmv) for a 10 s sensor time constant and 3.4 mW laser power delivered to the sensor module. PACS 42.62.Fi; 72.50.+b     

Ultra-sensitive carbon monoxide detection by using EC-QCL based quartz-enhanced photoacoustic spectroscopy

A quartz-enhanced photoacoustic spectroscopy (QEPAS) based sensor for carbon monoxide detection at ppbv levels was developed with a 4.65???m external-cavity quantum cascade laser operating both in continuous wave (cw) and pulsed modes. A?23-fold enhancement of the measured CO signal amplitude was obtained when water vapor, acting as a catalyst for vibrational energy transfer, was added to the targeted analyte mixture. In the cw mode, a noise-equivalent sensitivity (NES, 1??) of 2 ppbv was achieved at a gas pressure of 100?Torr, for 1-s lock-in amplifier (LIA) time constant (TC), which corresponds to a normalized noise equivalent absorption coefficient (NNEA) of $1.48\times 10^{-8}~\mathrm{cm}^{-1}\,\mathrm{W}/\sqrt{\mathrm{Hz}}$ . In the pulsed mode, the determined NES and NNEA were 46?ppbv and $1.07\times 10^{-8}~\mathrm{cm}^{-1}\,\mathrm{W}/\sqrt{\mathrm{Hz}}$ , respectively, for a 3-ms LIA TC at atmospheric pressure with a laser scan rate of 18?cm^-1/s and a 50?% duty cycle. An intercomparison between cw and pulsed QEPAS-based CO detection is also reported.     

Impact of humidity on quartz-enhanced photoacoustic spectroscopy based detection of HCN

The architecture and operation of a trace hydrogen cyanide (HCN) gas sensor based on quartz-enhanced photoacoustic spectroscopy and using a λ=1.53 μm telecommunication diode laser are described. The influence of humidity content in the analyzed gas on the sensor performance is investigated. A kinetic model describing the vibrational to translational (V–T) energy transfer following the laser excitation of a HCN molecule is developed. Based on this model and the experimental data, the V–T relaxation time of HCN was found to be (1.91±0.07)10^-3 s Torr in collisions with N₂ molecules and (2.1±0.2)10^-6 s Torr in collisions with H₂O molecules. The noise-equivalent concentration of HCN in air at normal indoor conditions was determined to be at the 155-ppbv level with a 1-s sensor time constant. PACS 82.80.Kq; 42.62.Fi     

Open-path measurement of ozone and methane gases using quartz-enhanced photoacoustic spectroscopy

We demonstrate a standoff system based on quartz-enhanced photoacoustic spectroscopy technique for the concentration measurements of atmospheric ozone and methane. The technique is a modified version of Photoacoustic spectroscopy. Two primary features of this technique are the employment of a tunable quantum cascade laser and a resonant quartz-crystal tuning fork detector. Both of these features facilitate simultaneous sensing of multiple molecular species. External-cavity quantum cascade laser having a spectral range from 7 to 10 micron is used. Diurnal concentration variations of methane and ozone are estimated for open-path up to 25 m. The ambient methane and ozone concentration maxima were observed to have values of 3.5 parts per million by volume and 140 parts per billion by volume, respectively. Finite-element mesh-based software is used to simulate the Eigen frequency of the tuning fork sensor. High-resolution transmission molecular spectroscopic database of atmospheric gases and the real-time gas concentration data from the Delhi Pollution Control Committee have been used as references.     

The SNR improvement for quartz-enhanced photoacoustic spectroscopy using wavelength calibration and fiber reflector

Wavelength calibration technique combined with a fiber reflector was used to improve the signal to noise ratio (SNR) of quartz-enhanced photoacoustic spectroscopy (QEPAS). A distributed feedback laser diode (DFB-LD), driven by sawtooth wave and high frequency sinusoidal wave, was used to excite the second harmonic signal of a quartz tuning fork (QTF) through laser-gas molecular interaction. Two collimators conducted the laser alignment through the spacing gap of QTF forks. Central wavelength of the DFB-LD was locked to the target gas absorption center by identifying the second harmonic signal maximum and applying calibration feedback on the driving current. The gas absorption center calibration and gas concentration measurements are conducted at a specific interval. The SNR of the photoacoustic signal was further acoustically enhanced by using a pair of on-beam acoustic resonators through increasing the photo-acoustic conversion efficient, and optically enhanced by using a fiber reflector to improve the laser power for photoacoustic signal excitation. The experimental results show that the SNR in wavelength calibration mode is 15 times higher than the conventional wavelength scanning mode and QEPAS signal with fiber reflector is 1.37 times stronger compared with that without a fiber reflector.     

A quartz-enhanced photoacoustic spectroscopy sensor for measurement of water vapor concentration in the air

A compact and highly linear quartz-enhanced photoacoustic spectroscopy(QEPAS)sensor for the measurement of water vapor concentration in the air is demonstrated.A cost-effective quartz tuning fork(QTF)is used as the sharp transducer to convert light energy into an electrical signal based on the piezoelectric effect,thereby removing the need for a photodetector.The short optical path featured by the proposed sensing system leads to a decreased size.Furthermore,a pair of microresonators is applied in the absorbance detection module(ADM)for QTF signal enhancement.Compared with the system without microresonators,the detected QTF signal is increased to approximately 7-fold.Using this optimized QEPAS sensor with the proper modulation frequency and depth,we measure the water vapor concentration in the air at atmospheric pressure and room temperature.The experimental result shows that the sensor has a high sensitivity of 1.058parts-per-million.     

基于微型非共振腔的石英增强光声光谱用于氦气纯度分析的实验研究

实验中设计了一种基于微型非共振腔的石英增强光声光谱痕量气体传感器, 用来检测非纯氦气中的痕量氨气浓度. 该传感器采用的微型非共振腔只在空间上限制声波扩散以达到增强信号目的, 而不是像传统微型共振腔一样依靠共振效应. 如此的设计使探测小分子无机气体的光谱测声器尺寸远远小于共振腔的配置而有利于准直. 不同气压下的信号和噪声也被研究, 用来优化传感器性能. 在这种配置下和27.7 kPa的最优气压下, 获得的最佳氨气探测灵敏度为463 ppb (1σ , 1 s积分时间), 相应的归一化噪声等效吸收系数为4.3×10^-9cm^-1W/√Hz. 关键词： 气体传感器 石英增强光声光谱 音叉式石英晶振 类氢气体纯度分析     

Ultrasensitive gas detection by quartz-enhanced photoacoustic spectroscopy in the fundamental molecular absorption bands region

A trace gas sensor based on quartz-enhanced photoacoustic spectroscopy with a quantum cascade laser operating at 4.55 m as an excitation source was developed. The sensor performance was evaluated for the detection of N₂O and CO. A noise-equivalent (1) sensitivity of 4 ppbv N₂O with 3 s response time to (1-1/e) of the steady-state level was demonstrated. The influence of the relevant energy transfer processes on the detection limits was analyzed. Approaches to improve the current sensor performance are also discussed. PACS 42.62.Fi; 43.35.Sx     

NO trace gas sensor based on quartz-enhanced photoacoustic spectroscopy and external cavity quantum cascade laser

A gas sensor based on quartz-enhanced photoacoustic detection and an external cavity quantum cascade laser was realized and characterized for trace nitric oxide monitoring using the NO R(6.5) absorption doublet at 1900.075 cm⁻¹. Signal and noise dependence on gas pressure were studied to optimize sensor performance. The NO concentration resulting in a noise-equivalent signal was found to be 15 parts per billion by volume, with 100 mW optical excitation power and a data acquisition time of 5 s.     

Application of a widely electrically tunable diode laser to chemical gas sensing with quartz-enhanced photoacoustic spectroscopy

A near-infrared diode laser with sample-grating distributed Bragg reflectors was used as a widely tunable spectroscopic source for multispecies chemical sensing. Quartz-enhanced photoacoustic spectroscopy was utilized to obtain high absorption sensitivity in a compact gas cell. CO2, H2O C2H2, and NH3 were monitored. A noise equivalent sensitivity of 8 x 10(-9) cm(-1) W(-1) Hz(-1/2)for NH3 detection was achieved, which corresponds to a NH3 mixing ratio of 4.4 parts in 10(6) by volume (ppmv) with a 1-s time constant and available 5.2-mW optical power in the gas cell.     

Continuous wave optical parametric oscillator for quartz-enhanced photoacoustic trace gas sensing

A continuous wave optical parametric oscillator, generating up to 300 mW idler output in the 3–4 μm wavelength region, and pumped by a fiber-amplified DBR diode laser is used for trace gas detection by means of quartz-enhanced photoacoustic spectroscopy (QEPAS). Mode-hop-free tuning of the OPO output over 5.2 cm^-1 and continuous spectral coverage exceeding 16.5 cm^-1 were achieved via electronic pump source tuning alone. Online monitoring of the idler wavelength, with feedback to the DBR diode laser, provided an automated closed-loop control allowing arbitrary idler wavelength selection within the pump tuning range and locking of the idler wavelength with a stability of 1.7×10^-3 cm^-1 over at least 30 min. Using this approach, we locked the idler wavelength at an ethane absorption peak and obtained QEPAS data to verify the linear response of the QEPAS signal at different ethane concentrations (100 ppbv-20 ppmv) and different power levels. The detection limit for ethane was determined to be 13 ppbv (20 s averaging), corresponding to a normalized noise equivalent absorption coefficient of 4.4×10^-7 cm^-1  W/Hz^1/2. PACS 42.55.Wd; 42.65.Yj; 42.62.Fi     

Application of a broadband blue laser diode to trace NO2 detection using off-beam quartz-enhanced photoacoustic spectroscopy

We applied for the first time, to our knowledge, broadband off-beam quartz-enhanced photoacoustic spectroscopy (BB-OB-QEPAS) to trace NO2 detection using a broadband blue laser diode centered at 450?nm. A detection limit of 18?ppbv (parts in 10(9) by volume) for NO2 in N2 at atmospheric pressure was achieved with an average laser power of 7?mW at a 1?s integration time, which corresponds to a 1?σ normalized noise equivalent absorption coefficient of 4.1×10(-9) cm(-1)?W=Hz(1=2). An Allan variance analysis was performed to investigate the long-term stability of the BB-OB-QEPAS-based NO2 sensor.     

Time-resolved photoacoustic spectroscopy using fiber Bragg grating acoustic transducers

An acoustic transducer based on a fiber Bragg grating (FBG) is presented and characterized for use in time-resolved laser-induced photoacoustic spectroscopy (PAS) on solid samples. The photoacoustic wave was generated by pulsed laser excitation of immobilized carbon black or erbium oxide powder, and detected by recording either the transmission or reflection spectrum of a clamped fiber Bragg grating (FBG). The characterization of the FBGs photoacoustic response is based on the experimental comparison with a static lateral strain source and on theoretical analysis using the piecewise-uniform approach to photoelastic theory. The temporal resolution of the response is determined by the arrangement of the FBG with respect to the source of the acoustic wave and is better than 150 ns, as was verified in a deconvolution analysis.The method has not only a fast time response but also is simple, inexpensive, and accurate as indicated by the good agreement of the experimental photoacoustic spectrum with previous measurements.